CN101668427A - fungicide mixtures - Google Patents

fungicide mixtures Download PDF

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Publication number
CN101668427A
CN101668427A CN200880013596A CN200880013596A CN101668427A CN 101668427 A CN101668427 A CN 101668427A CN 200880013596 A CN200880013596 A CN 200880013596A CN 200880013596 A CN200880013596 A CN 200880013596A CN 101668427 A CN101668427 A CN 101668427A
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compound
mixture
plant
reactive compound
formula
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D·弗斯特
C·赖内克
F·维尔纳
E·哈登
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BASF SE
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BASF SE
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to fungicide mixtures containing, as active constituents: 1) metconazole of formula (I), and 2) prochloraz of formula (II), in synergistically effective quantities, and to meanscontaining said mixtures.

Description

Fungicidal mixtures
The present invention relates to Fungicidal mixture, it comprises following compound as active component with the Synergistic effective dose:
1) the ring penta azoles bacterium (metconazole) of formula I:
Figure G2008800135961D00011
With
2) Prochloraz of formula II (prochloraz):
Figure G2008800135961D00012
In addition, the present invention relates to a kind of mixture methods for fighting harmful mushrooms of using Compound I and Compound I I, Compound I and Compound I I preparation in such mixture purposes and the composition that comprises these mixtures.
The ring penta azoles bacterium that is called component 1 above is (1RS, 5RS; 1RS, 5SR)-5-(4-benzyl chloride base)-2,2-dimethyl-1-(1H-1,2,4-triazol-1-yl methyl) cyclopentanol, its preparation and to the effect of harmful fungoid by document known (EP-A 267778).
The reactive compound Prochloraz that is called component 2 above is N-propyl group-N-[2-(2,4, the 6-Trichlorophenoxy) ethyl] imidazoles-1-formamide, its preparation and to the effect of harmful fungoid known equally (US3,991,071).
EP-A 0951831 discloses a kind of concentrated liquid Fungicidal composition, and it is by carrier, azole (also comprising ring penta azoles bacterium), form as other Fungicidally active components, solubilizer and the dispersant of suspension in small, broken bits.Other Fungicidally active components of being mentioned are a queue of fungicide that also comprises Prochloraz.The mixture of unique description is ring penta azoles bacterium and imines bacterium (kresoxim-methyl) and tpn (chlorothalonil).The goal of the invention that forms the basis of this application is the stable preparaton altogether that concentrates.
Consider the rate of application that reduces known compound and widen its activity profile, purpose of the present invention is provided at reactive compound and uses under the situation that total amount reduces harmful fungoid, and especially some indication demonstrates and improves active mixture.
Therefore, we have found the defined mixture of beginning.In addition, have been found that with using independent compound and compare that simultaneously, promptly unite or separate administration Compound I and Compound I I, perhaps administered compound I and Compound I I allow to prevent and treat better harmful fungoid (Synergistic mixture) successively.Simultaneously, promptly associating or separate administration Compound I and Compound I I have increased Fungicidally active in super adduction mode.
The mixture of Compound I and Compound I I, perhaps simultaneously, promptly the associating or separately use Compound I and Compound I I to be characterised in that to plant, especially pulses leguminous plants has the effect that promotes growth and increase output and to the plant pathogenic fungi of wide region, (synonym: fungi Oomycete (Oomycetes)) has excellent effectiveness especially to be selected from Ascomycetes (Ascomycetes), deuteromycetes (Deuteromycetes), Basidiomycetes (Basidiomycetes) and Peronosporomycetes.In them some are effectively collaborative and can be used as blade face fungicide, seed dressing is used for crop protection with fungicide and soil fungicide.
They are even more important to a large amount of fungies of control in various crop plants such as banana, cotton, vegetable variety (for example cucumber, beans and cucurbitaceous plant), barley, dogstail, oat, coffee, potato, corn, fruit plant, rice, rye, soybean, tomato, grape vine, wheat, ornamental plants, sugarcane and a large amount of seed.
They advantageously are fit to prevent and treat the following plants disease:
● the Alternaria on vegetable variety, oilseed rape, sugar beet, fruit and the rice (Alternaria), for example epidemic disease chain lattice spores morning (A.solani) on potato and the tomato or chain lattice spore (A.alternata),
● the Aphanomyces on sugar beet and the vegetable variety (Aphanomyces),
● the Ascochyta on cereal class and the vegetable variety (Ascochyta),
● flat navel Helminthosporium (Bipolaris) on corn, cereal class, rice and the lawn and interior navel Helminthosporium (Drechslera), the flat navel of the maize on the corn spore (D.maydis) of wriggling for example,
● the standing grain powdery mildew on the cereal class (Blumeria graminis) (powdery mildew),
● the Botrytis cinerea on strawberry, vegetable variety, flowers and the grape vine (Botrytis cinerea) (gray mold),
● the lettuce dish stalk mould (Bremia lactucae) on the lettuce,
● the Cercospora on corn, soybean, rice and the sugar beet (Cercospora),
● cochliobolus on corn, cereal class, the rice belongs to (Cochliobolus), the standing grain cochliobolus on the cereal class (Cochliobolus sativus) for example, and the palace portion cochliobolus (Cochliobolusmiyabeanus) on the rice,
● the perverse dish spore on soybean and the cotton belongs to (Colletotricum),
● the interior navel Helminthosporium (Drechslera) on corn, cereal class, rice and the lawn, nuclear cavity Pseudomonas (Pyrenophora), wriggle D.tritici-repentis on spore (D.teres) or the wheat of navel in the barley filigree on the barley for example,
● the Eschka (Esca) on the grape vine that causes by Phaeoacremonium chlamydosporium, Ph.Aleophilum and Formitiporapunctata (synonym spot hole Phellinus (Phellinus punctatus)),
● the grape Elsinochrome on the grape vine (Elsinoe ampelina),
● the prominent navel Helminthosporium (Exserohilum) on the corn,
● two spore powdery mildews (Erysiphe cichoracearum) on the cucumber and monofilament shell powdery mildew (Sphaerotheca fuliginea),
● Fusarium on each plant species (Fusarium) and Verticillium (Verticillium), for example fusarium graminaria (F.graminearum) on the cereal class or the sharp sickle spore (F.oxysporum) on machete sickle spore (F.culmorum) or various plants such as the tomato
● the gaeumannomyce on the cereal class (Gaeumanomyces graminis),
● the Gibberella on cereal class and the rice (Gibberella) (for example gibberella fujikuroi on the rice (Gibberellafujikuroi)),
● the apple anthrax bacteria on grape vine and the other plant (Glomerella cingulata),
● the Grainstaining complex on the rice,
● the Guignardia budwelli on the grape vine,
● the Helminthosporium on corn and the rice (Helminthosporium),
● the foxiness on the grape vine is intended Isaria (Isariopsis clavispora),
● the Michrodochium nivale on the cereal class,
● the mycosphaerella on cereal class, banana and the peanut (Mycosphaerella), for example standing grain green-ball chamber bacterium (M.graminicola) on the wheat or the Fijian ball chamber bacterium (M.fijiensis) on the banana,
● the Peronospora (Peronospora) on cabbage and the bulb plant, for example rape downy mildew (P.brassicae) on the cabbage or the shallot downy mildew (P.destructor) on the onion,
● yam bean layer rest fungus (Phakopsara pachyrhizi) on the soybean and mountain horseleech layer rest fungus (Phakopsara meibomiae),
● the Phomopsis on soybean and the sunflower (Phomopsis), the grape on the grape vine is given birth to single shaft mould (P.viticola),
● the phytophthora infestans on potato and the tomato (Phytophthora infestans),
● the Phytophthora on each plant species (Phytophthora), the Phytophthora capsici on the green pepper (P.capsici) for example,
● the grape on the grape vine is given birth to single shaft mould (Plasmopara viticola),
● the apple mildew bacterium on the apple (Podosphaera leucotricha),
● the rotten germ (Pseudocercosporella herpotrichoides) of the wheat-based on the cereal class,
● the false Peronospora (Pseudoperonospora) on each plant species, for example humulus grass vacation white (P.Humili) on false downy mildew (P.Cubensis) of the Cuba on the cucumber or the lupulus,
● the Pseudopezicula tracheiphilai on the grape vine,
● the Puccinia on each plant species (Puccinia), for example the wheat handle rest fungus (P.triticina) on the cereal class, bar shaped handle rust (P.striformins), barley handle rust (P.hordei) or puccinia graminis (P.graminis), or the Asparagus handle rust (P.asparagi) on the asparagus)
● the Pyricularia oryzae on the rice (Pyricularia oryzae), Bamboo grass wood photovoltaicing leather bacteria (Corticium sasakii), broom stalk Cylindrocarpon (Sarocladium oryzae), sheath rot of rice plant (S.attenuatum), rice leaf smut (Entyloma oryzae)
● the piricularia oryzae on lawn and the cereal class (Pyricularia grisea),
● the pythium on lawn, rice, corn, cotton, oilseed rape, sunflower, sugar beet, vegetable variety and the other plant (Pythium), the ultimate pythium spp (P.ultiumum) on each plant species for example, melon and fruit corruption on the lawn mould (P.aphanidermatum)
● the Rhizoctonia (Rhizoctonia) on cotton, rice, potato, lawn, corn, oilseed rape, sugar beet, vegetable variety and each plant species, the miliary damping-off germ (R.solani) on beet and each plant species for example,
● the rye beak spore (Rhynchosporium secalis) on barley, rye and the triticale,
● the Sclerotinia on oilseed rape and the sunflower (Sclerotinia),
● wheat septoria on the wheat (Septoria tritici) and the many spores of clever withered shell (Stagonosporanodorum),
● the grape snag shell on the grape vine (Erysiphe (synonym Uncinula) necator),
● the Setospaeria on corn and the lawn belongs to,
● the silk axle smut (Sphacelotheca reilinia) on the corn,
● the Thiclaviopsis on soybean and the cotton (Thievaliopsis),
● the Tilletia on the cereal class (Tilletia),
● the Ustilago on cereal class, corn and the sugarcane (Ustilago), the Ustilago maydis on the corn (U.maydis) for example,
● the Venturia on apple and the pears (Venturia) (scab), for example apple scab on the apple (V.inaequalis).
In addition, the mixture of Compound I and Compound I I is suitable for preventing and treating the product of harmful fungoid with protective material (as timber, paper, lacquer dispersion, fiber or fabric) and protection storage.In wood protection, should note following harmful fungoid especially: Ascomycetes fungi such as line mouth shell belong to (Ophiostoma spp.), long beak shell belongs to (Ceratocystis spp.), Aureobasidium pullulans (Aureobasidium pullulans), Sclerophoma spp., Chaetomium (Chaetomium spp.), Humicola (Humicola spp.), Peter's shell belongs to (Petriella spp.), the mould genus of pieces (Trichurus spp.); Basidiomycetes fungi such as cellar fungus belong to (Coniophora spp.); Coriolus Qu61 (Coriolus spp.); sticking gill fungus belongs to (Gloeophyllum spp.); Lentinus (Lentinus spp.); Pleurotus (Pleurotus spp.); hole genus (Poria spp.) crouches; Merulius (Serpula spp.) and cheese Pseudomonas (Tyromyces spp.); deuteromycetes fungi such as aspergillus (Aspergillus spp.); Cladosporium (Cladosporium spp.); Penicillium (Penicillium spp.); trichoderma (Trichoderma spp.); Alternaria (Alternariaspp.); paecilomyces (Paecilomyces spp.) and Zygomycetes (Zygomycetes) fungi such as mucor (Mucor spp.) should be noted following yeast in this external material protection: candida (Candidaspp.) and saccharomyces cerevisiae (Saccharomyces cerevisae).
In addition, the mixture of Compound I and Compound I I can be used for the crop plant because of breeding herbicide-tolerant, fungicide or the insecticide effect that comprises gene engineering method.
Mixture of the present invention for example can be used for genetically modified plants (EP-A 0242236, EP-A 0242246, WO 92/00377, EP-A 0257993, US 5 that sulfonylurea, imidazolone type, careless ammonium phosphine (glufosinate-ammonium) or glyphosate isopropyl amine salt (glyphosate-isopropyl-ammonium) weed killer herbicide and similar reactive compound are had tolerance, 013,659).Perhaps they can be used for the genetically modified crops plant, the wool of the bacillus thuringiensis,Bt that can produce (Bacillusthuringiensis) toxin (Bt toxin) for example, thus give the tolerance of plant to some insect (EP-A 0142924, EP-A 0193259).
In addition, mixture of the present invention can also be used to handle the plant with change performance.They for example can produce mutant by the conventional breeding method and produce.It is also known that the reorganization modification (WO 92/11376, WO 92/14827, WO91/19806) of the crop plant that is used for changing the starch that plant synthesizes.In addition, can also be with mixture process crop plant of the present invention to produce modified fat acid (WO 91/13972).
Compound I and II can be simultaneously, i.e. associating or separate administration or use successively, under the situation of separate administration order of administration usually to the result of prophylactico-therapeutic measures without any influence.
Maybe advantageously in reactive compound I and II, add one or more other reactive compounds in some cases.
Following can being used to possible combination is described with the fungicide that The compounds of this invention is united use, but do not limit them:
Azole
-triazole type: Bitertanol (bitertanol), bromuconazole (bromuconazole), cyproconazole (cyproconazole) Difenoconazole (difenoconazole), alkene azoles alcohol (diniconazole), IMAZALIL (enilconazole), oxole bacterium (epoxiconazole), RH-7592 (fenbuconazole), Flusilazole (flusilazole), Fluquinconazole (fluquinconazole), Flutriafol (flutriafol), own azoles alcohol (hexaconazole), acid amides azoles (imibenconazole), cycltebuconazole (ipconazole), nitrile bacterium azoles (myclobutanil), penconazole (penconazole), propiconazole (propiconazole), prothioconazoles (prothioconazole), simeconazoles (simeconazole), Tebuconazole (tebuconazole), fluorine ether azoles (tetraconazole), triadimenol (triadimenol), triazolone (triadimefon), triticonazole (triticonazole);
-imidazoles: cyanogen frost azoles (cyazofamid), press down mould azoles (imazalil), pefurazoate (pefurazoate), fluorine bacterium azoles (triflumizole);
-benzimidazole: benomyl (benomyl), carbendazim (carbendazim), furidazol (fuberidazole), thiabendazole (thiabendazole);
-other: Guardian (ethaboxam), kobam (etridiazole), hydroxyisoxazole (hymexazole); Strobilurins class (strobilurins)
-nitrile Fluoxastrobin (azoxystrobin), ether bacterium amine (dimoxystrobin), Enestroburin (enestroburin), fluoxastrobin (fluoxastrobin), imines bacterium (kresoxim-methyl), fork phenalgin acid amides (metominostrobin), ZEN 90160 (picoxystrobin), pyraclostrobin (pyraclostrobin), oxime bacterium ester (trifloxystrobin), orysastrobin (orysastrobin), (2-chloro-5-[1-(3-methyl benzyloxy imino) ethyl] benzyl) methyl carbamate, (2-chloro-5-[1-(6-picoline-2-base methoxyimino) ethyl] benzyl) methyl carbamate, 2-(neighbour-(2,5-dimethyl phenoxy methylene) phenyl)-3-methoxy-methyl acrylate;
Carboxyl acylamide
-carboxanilides class: M 9834 (benalaxyl), benodanil (benodanil), Boscalid (boscalid), carboxin (carboxin), third oxygen goes out and embroiders amine (mepronil), methuroxam (fenfuram), fenhexamid (fenhexamid), flutolanil (flutolanil), furan pyrazoles spirit (furametpyr), metalaxyl (metalaxyl), fenfuram (ofurace) Evil frost spirit (oxadixyl), oxycarboxin (oxycarboxin), pyrrole metsulfovax (penthiopyrad), thifluzamide (thifluzamide), tiadinil (tiadinil), N-(4 '-bromo biphenyl-2-yl)-4-difluoromethyl-2-methylthiazol-5-formamide, N-(4 '-trifluoromethyl-biphenyl-2-yl)-4-difluoromethyl-2-methylthiazol-5-formamide, N-(4 '-chloro-3 '-fluorine biphenyl-2-yl)-4-difluoromethyl-2-methylthiazol-5-formamide, N-(3 ', 4 '-two chloro-4-fluorine biphenyl-2-yls)-3-difluoromethyl-1-methylpyrazole-4-formamide, N-(2-cyano-phenyl)-3,4-two chloroisothiazoles-5-formamide;
-carboxylic acid morpholine thing: dimethomorph (dimethomorph), flumorph (flumorph);
-benzamides: fluorine biphenyl bacterium (flumetover), fluopicolide (fluorine pyrrole bacterium amine (picobenzamid)), zoxamide (zoxamide);
-other carboxylic acid amides: carpropamide (carpropamid), two chlorine zarilamid (diclocymet), mandipropamid amine (mandipropamid), N-(2-(4-[3-(4-chlorphenyl) third-2-alkynyloxy group]-3-methoxyphenyl) ethyl)-2-methane sulfonyl amino-3-methylbutyryl amine, N-(2-(4-[3-(4-chlorphenyl) third-2-alkynyloxy group]-the 3-methoxyphenyl) ethyl)-2-ethane sulfuryl amino-3-methylbutyryl amine;
The nitrogen heterocyclic ring based compound
-pyridines: pyrifenox (pyrifenox), 3-[5-(4-chlorphenyl)-2,3-dimethyl isoxazole alkane-3-yl] pyridine;
-miazines: the phonetic bacterium spirit of sulphur (bupirimate), ferimzone (ferimzone), fenarimol (fenarimol), mepanipyrim (mepanipyrim), nuarimol (nuarimol), pyrimethanil (pyrimethanil);
-piperazines: triforine (triforine);
-pyroles: Fu Evil bacterium (fludioxonil), fenpiclonil (fenpiclonil);
-morpholine class: 4-dodecyl-2,6-thebaine (aldimorph), dodemorfe (dodemorph), butadiene morpholine (fenpropimorph), tridemorph (tridemorph);
-dicarboximide class: different third fixed (iprodione), the sterilization profit (procymidone), vinclozolin (vinclozolin);
-other: thiadiazoles element (acibenzolar-S-methyl), anilazine (anilazine), captan (captan), difoltan (captafol), dazomet (dazomet), diclomezine (diclomezine), zarilamid (fenoxanil), folpet (folpet), fenpropidin (fenpropidin) azolactone bacterium (famoxadone), Fenamidone (fenamidone), different thiophene bacterium ketone (octhilinone), probenazole (probenazole), the third oxygen quinoline (proquinazid), pyroquilon (pyroquilon), quinoxyfen (quinoxyfen), tricyclazole (tricyclazole), 5-chloro-7-(4-methyl piperidine-1-yl)-6-(2,4, the 6-trifluorophenyl)-[1,2,4] triazol [1,5-a] pyrimidine, 2-butoxy-6-iodo-3-propyl group chromene-4-ketone, N, N-dimethyl-3-(3-bromo-6-fluoro-2 methyl indole-1-sulfonyl)-[1,2,4] triazole-1-sulfonamide;
Carbamate and dithiocar-bamate
-dithiocarbamates: ferbam (ferbam), mancozeb (mancozeb), maneb (maneb), Carbatene (metiram), metham-sodium (metam), propineb (propineb), tmtd (thiram), zineb (zineb), ziram (ziram);
-Carbamates: the mould prestige of second (diethofencarb), flubenthiavalicarb, iprovalicarb (iprovalicarb), hundred dimension spirit (propamocarb), 3-(4-chlorphenyl)-3-(different third oxygen carbonylamino of 2--3-methylbutyryl amino) methyl propionates, N-(1-(1-(4-cyano-phenyl) ethane sulfonyl) fourth-2-yl) carbamic acid 4-fluorophenyl ester;
Other fungicides
-guanidine class: dodine (dodine), biguanide spicy acid salt (iminoctadine), guazatine (guazatine);
-antibiotics: spring thunder element (kasugamycin), Polyoxin (polyoxins), streptomycin (streptomycin), jinggangmeisu (validamycin A);
-organo-metallic compound class: triphenyltin salt;
-sulfur heterocyclic ring based compound: Isoprothiolane (isoprothiolane), Delan (dithianon);
-organic phosphorus compound: Hinosan (edifenphos), fosetyl (fosetyl), ethyl phosphine aluminium (fosetyl-aluminum), iprobenfos (iprobenfos), Ppyrazophos (pyrazophos), tolelofos-methyl (tolclofos-methyl), phosphorous acid and salt thereof;
-organochlorine compound: thiophanate methyl (thiophanate-methyl), tpn (chlorothalonil), Euparen (dichlofluanid), tolyfluanid (tolylfluanid), flusulfamide (flusulfamide), Rabcide (phthalide), hexachloro-benzene (hexachlorobenzene), Pencycuron (pencycuron), pcnb (quintozene);
-nitrophenyl derivative: binapacryl (binapacryl), karathane (dinocap), dinobuton (dinobuton);
-inorganic active compound: bordeaux mixture (Bordeaux mixture), Schweinfurt green, Kocide SD, Cupravit, basic copper sulfate, sulphur;
-other luxuriant amine of: Luo Evil (spiroxamine), cyflufenamid (cyflufenamid), cymoxanil (cymoxanil), metrafenone (metrafenone).
Reactive compound can also its receivable agricultural salt form use.Be suitable for normally alkali metal or alkali salt such as sodium, potassium or the calcium salt of this purpose.
Compound I and Compound I I are usually with 100: 1-1: 100, preferred 20: 1-1: 20, especially 10: 1-1: 10 weight ratio is used.
Needing, can be 20 with the ratio of Compound I: 1-1: 20 add other active components.
Depend on the type and the required effect of compound, the rate of application of mixture of the present invention is 5-2000g/ha, preferred 50-900g/ha, especially 50-750g/ha.
Correspondingly, the rate of application of Compound I is generally 1-1000g/ha, preferred 10-900g/ha, especially 20-750g/ha.
Correspondingly, the rate of application of reactive compound II is generally 1-2000g/ha, preferred 10-900g/ha, especially 40-500g/ha.
For example be generally the 1-1000g/100kg seed, preferred 1-750g/100kg, especially 5-500g/100kg by the rate of application of seed dusting, dressing or immersion being handled the mixture that uses in the seed.
When being used for the product of protective material or storage, the amount of application of reactive compound depends on type and the required effect of using the zone.Common amount of application for example is every cubic metre of processed material 0.001g-2kg in protective material, preferred 0.005g-1kg reactive compound.
Methods for fighting harmful mushrooms by before or after the plant seeding or before or after plant emerges to seed, plant or soil spraying or dusting separates or the mixture of co-administered Compound I and Compound I I or Compound I and Compound I I carries out.
Mixture of the present invention or Compound I and Compound I I can change into conventional preparaton, for example solution, emulsion, suspension, pulvis, powder, paste and particle.Type of service depends on the specific purpose that is intended to; Should guarantee the meticulous and distribution equably of The compounds of this invention in each case.
Preparaton prepares in a known way, for example prepares by reactive compound is mixed with solvent and/or carrier, and the words that need are used emulsifier and dispersant.Solvent/the auxiliary agent suitable to this purpose is mainly:
-water, arsol (as Solvesso product, dimethylbenzene), paraffin (as mineral oil fractions), alcohols (as methyl alcohol, butanols, amylalcohol, benzylalcohol), ketone (as cyclohexanone, gamma-butyrolacton), pyrrolidones (NMP, NOP), acetic acid esters (ethylene acetate), dihydroxylic alcohols, fatty acid dimethylformamide, fatty acid and fatty acid ester.Can also use solvent mixture in principle.
-carrier is as natural minerals (as kaolin, clay, talcum, chalk) that grinds and the synthetic mineral (as silica in small, broken bits, silicate) that grinds; Emulsifier such as nonionic and anion emulsifier (as polyoxyethylene aliphatic alcohol ether, alkylsulfonate and arylsulphonate) and dispersant such as lignin sulfite waste liquor and methylcellulose.
Suitable surfactant is a lignosulphonic acid, naphthalene sulfonic acids, phenolsulfonic acid, the alkali metal salt of dibutyl naphthalene sulfonic acids, alkali salt and ammonium salt, alkylaryl sulfonates, alkyl sulfate, alkylsulfonate, aliphatic alcohol sulfate, fatty acid and sulphated fatty alcohol glycol ether, the condensation product of sulfonated naphthalene and naphthalene derivatives and formaldehyde in addition, the condensation product of naphthalene or naphthalene sulfonic acids and phenol and formaldehyde, NONIN HS 240, the ethoxylation isooctylphenol, octyl phenol, nonyl phenol, the alkyl phenyl polyglycol ether, tributyl phenyl polyglycol ether, three stearyl phenyl polyglycol ethers, alkyl aryl polyether alcohol, pure and mild fatty alcohol/ethylene oxide condensation product, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylation polyoxypropylene, laruyl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite waste liquor and methylcellulose.
Being suitable for preparing directly, the material of spray solution, emulsion, paste or oil dispersion is that mid-boiling point arrives high boiling mineral oil fractions such as kerosene or diesel oil, the oil that also has coal tar and plant or animal origin in addition, aliphatic series, ring-type and aromatic hydrocarbon, for example toluene, dimethylbenzene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, methyl alcohol, ethanol, propyl alcohol, butanols, cyclohexanol, cyclohexanone, isophorone, intensive polar solvent, for example methyl-sulfoxide, N-Methyl pyrrolidone and water.
But powder, broadcast sowing with material and dusting product and can prepare by active substance is mixed with solid carrier or grinds simultaneously.
Particle such as coated particle, impregnated granules and homogeneous particle can be by preparing reactive compound and solid carrier adhesion.The example of solid carrier is that ore deposit soil is as silica gel, silicate, talcum, kaolin, activated clay (attaclay), lime stone, lime, chalk, bole, loess, clay, dolomite, diatomite, calcium sulphate, magnesium sulfate, magnesia, the synthetic material that grinds, fertilizer such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and the product of plant origin such as flour, bark powder, wood powder and shuck powder, cellulose powder and other solid carrier.
Preparaton comprises 0.01-95 weight % usually, the reactive compound of preferred 0.1-90 weight %.Reactive compound is with 90-100%, and the purity of preferred 95-100% (according to the NMR spectrum) is used.
Under classify the preparaton example as:
1. the product of dilute with water
A water-soluble concentrate (SL, LS)
10 weight portion reactive compounds are dissolved in 90 weight parts waters or the water-soluble solvent.Perhaps, add wetting agent or other auxiliary agent.Reactive compound is through water dilution dissolving.Obtain the preparaton that reactive compound content is 10 weight % in this way.
The dispersed concentrate (DC) of B
Be dissolved in 20 weight portion reactive compounds in the 70 weight portion cyclohexanone and add 10 weight portion dispersant such as PVP(polyvinyl pyrrolidone).Dilute with water obtains dispersion.Reactive compound content is 20 weight %.
The emulsible concentrate of C (EC)
Be dissolved in 15 weight portion reactive compounds in the 75 weight portion dimethylbenzene and add calcium dodecyl benzene sulfonate and castor oil ethoxylate (being 5 weight portions in each case).Dilute with water obtains emulsion.The reactive compound content of this preparaton is 15 weight %.
D emulsion (EW, EO, ES)
Be dissolved in 25 weight portion reactive compounds in the 35 weight portion dimethylbenzene and add calcium dodecyl benzene sulfonate and castor oil ethoxylate (being 5 weight portions in each case).Introduce this mixture in 30 weight parts waters and make equal phase emulsion by mulser (for example Ultraturrax).Dilute with water obtains emulsion.The reactive compound content of this preparaton is 25 weight %.
E suspension (SC, OD, FS)
In the ball mill that stirs, 20 weight portion reactive compounds are pulverized and added 10 weight portion dispersants and wetting agent and 70 weight parts waters or organic solvent, obtain meticulous reactive compound suspension.Dilute with water obtains stable reactive compound suspension.Reactive compound content in this preparaton is 20 weight %.
F water-dispersible granule and water-soluble granular (WG, SG)
With 50 weight portion reactive compound fine gtindings and add 50 weight portion dispersant and wetting agents, be made into water dispersible or water-soluble granular by commercial plant (as extruder, spray tower, fluid bed).Dilute with water obtains stable active compound dispersion or solution.The reactive compound content of this preparaton is 50 weight %.
G water dispersible pow-ders and water-soluble powder (WP, SP, SS, WS)
75 weight portion reactive compounds are ground in the rotor-stator grinding machine and add 25 weight portion dispersants, wetting agent and silica gel.Dilute with water obtains stable active compound dispersion or solution.The reactive compound content of this preparaton is 75 weight %.
H gel formulation (GF)
At grinding in ball grinder 20 weight portion reactive compounds, 10 weight portion dispersants, 1 weight portion gelling agent and 70 weight parts waters or organic solvent, obtain thin suspension.Dilute with water obtains the stable suspension that reactive compound content is 20 weight %.
2. the product of using without dilution
But I dusting powder (DP, DS)
Fully mix with 5 weight portion reactive compound fine gtindings and with 95 weight portions kaolin in small, broken bits.But this obtains the dusting product that reactive compound content is 5 weight %.
J particle (GR, FG, GG, MG)
With 0.5 weight portion reactive compound fine gtinding and in conjunction with 99.5 weight portion carriers.Current methods be extrude, atomized drying or bed process.This obtains the particle of using without dilution that reactive compound content is 0.5 weight %.
K ULV solution (UL)
10 weight portion reactive compounds are dissolved in 90 weight portion organic solvents such as the dimethylbenzene.This obtains the product of using without dilution that reactive compound content is 10 weight %.
For seed treatment, use water-soluble concentrate (LS), suspension (FS) usually but dusting powder (DS), water dispersible and water-soluble powder (WS, SS), emulsion (ES), emulsible concentrate (EC) and gel formulation (GF).These preparatons can be applied to the form of not diluted on the seed, perhaps preferably use with the form of dilution.Use and to carry out prior to seeding.
Reactive compound can be directly, with its preparaton form or type of service prepared therefrom (but as directly spray solution, powder, suspension or dispersion, emulsion, oil dispersion, paste dusting product, broadcast sowing), by spraying, atomizing, dusting, broadcast sowing or water and use with material or particle.Type of service depends on the purpose that is intended to fully; The best that should always guarantee reactive compound of the present invention may distribute.
Moisture type of service can be by adding entry by emulsible concentrate, paste or wettable powder (spraying powder, oil dispersion) preparation.Be preparation emulsion, paste or oil dispersion, can be with this material directly or be dissolved in back homogenizing in water in oil or the solvent by wetting agent, tackifier, dispersant or emulsifier.Yet, can also prepare comprise active substance, wetting agent, tackifier, dispersant or emulsifier and if possible solvent or oil concentrate, this concentrate is suitable for dilute with water.
Promptly can in relative broad range, change with the activity compound concentration in the preparation.They are generally 0.0001-10%, preferred 0.01-1%.
Reactive compound also can successfully be used for ultra low volume method (ULV), wherein can use to comprise the preparaton that surpasses 95 weight % reactive compounds, or even use the reactive compound that does not contain additive.
Can add various types of oil, wetting agent, adjuvant, weed killer herbicide, fungicide, other insecticides and bactericide in reactive compound, suitable words also add (bucket mixes) before being close to use.These reagent can be with 1: 100-100: 1, preferred 1: 10-10: 1 weight ratio adds in the present composition.
Application Example
The fungicidal action of compound and mixture can be confirmed by following test:
The reactive compound preparation
Use solvent/emulsifier volume ratio is that 99: 1 acetone and/or methyl-sulfoxide unites reactive compound or separate and make the stock solution that comprises the 25mg reactive compound and be made into 10ml with the mixture of emulsifier WettolEM 31 (wetting agent based on ethoxylated alkylphenol with emulsification and peptizaiton).Then this mixture water is made into 100ml.Dilute this stock solution to following activity compound concentration with described solvent/emulsifier/aqueous mixtures.
Application Example 1-is to the activity of the green pepper gray mold that caused by Botrytis cinerea (Botrytis cinerea), and protectiveness was used in 1 day
The green pepper rice shoot is sprayed to the drip point with activity compound concentration aqueous suspension as described below behind the 2-3 sheet leaf that reaches full growth out.To handle plant in second day is spore suspension inoculation in 2% the biological malt water solution with Botrytis cinerea in concentration.Then test plant is placed the dark climate regulation chamber of 22-24 ℃ and high atmospheric humidity.Can the percentage naked eyes after 5 days measure the fungal infection degree on the leaf.
Table 1
Reactive compound/reactive compound combination Concentration (ppm) Ratio Observed effectiveness (%) The effectiveness (%) of using the Colby formula to calculate Synergistic function Synergistic degree (%)
Encircle penta azoles bacterium ??0.016 ??0
Prochloraz ??0.25 ??0
Encircle penta azoles bacterium Prochloraz ??0.016??0.25 ??1∶16 ??50 ??0 Be ??50
Application Example 2-on wheat to the protection activity of Puccinia recondita f. sp. tritici (Puccinia recondita) (wheat leaf rust)
The leaf of potted plant wheat rice shoot is sprayed to the drip point with activity compound concentration aqueous suspension as described below.The plant that to handle in second day inoculates with the spore suspension of wheat leaf rust bacterium (Puccinia recondita f. sp. tritici).Under 20-22 ℃, plant was placed on then in the chamber of high atmospheric humidity (90-95%) 24 hours.Spore germination and germ tube are penetrated in the leaf texture during this period.Second day sends test plant in the greenhouse back to and be 20-22 ℃ in temperature is to cultivate under the 65-70% 7 days with relative atmospheric humidity again.Naked eyes are measured the development degree of rust fungi on leaf then.
Table 2
Reactive compound/reactive compound combination Concentration (ppm) Ratio Observed effectiveness (%) The effectiveness (%) of using the Colby formula to calculate Synergistic function Synergistic degree (%)
Encircle penta azoles bacterium ?0.25 ??13
Prochloraz ?4 ??0
Encircle penta azoles bacterium Prochloraz ?0.25?4 ??1∶16 ??38 ??13 Be ??25
The leaf area percentage that infects that naked eyes are measured changes into the effectiveness of representing with the % with respect to untreated control.
Use the Abbot formula to render a service (E) by following calculating:
E＝(1-α/β)·100
α corresponding to the fungal infection percentage of handling plant and
β is corresponding to the fungal infection percentage of (contrast) plant of being untreated.
Effectiveness is that 0 infecting of plant of expression processing is on close level in untreated check plant; Effectiveness is that 100 expression processing plants are infected.
The expection of reactive compound combination render a service use Colby formula (Colby, S.R. " calculates the Synergistic and the antagonism response of combinations of herbicides ", Weeds (weeds), 15, the 20-22 pages or leaves, 1967) determine and with the effectiveness of observing relatively.
Colby formula: E=x+y-xy/100
Expection when the E working concentration is the mixture of the reactive compound A of a and b and B is renderd a service, represents with % with respect to untreated control,
Effectiveness when the x working concentration is the reactive compound A of a is represented with the % with respect to untreated control,
Effectiveness when the y working concentration is the reactive compound B of b is represented with the % with respect to untreated control.
Result of the test in the table 1 and 2 shows, owing to exist synergistic function, the activity of mixture of the present invention to be significantly higher than the activity of using the expection of Colby formula.

Claims (11)

1. Fungicidal mixture, it comprises following compound as active component with the Synergistic effective dose:
1) the ring penta azoles bacterium of formula I:
Figure A2008800135960002C1
With
2) Prochloraz of formula II:
Figure A2008800135960002C2
2. according to the Fungicidal mixture of claim 1, with 100: 1-1: 100 weight ratio comprises formula I compound and formula II compound.
3. according to the Fungicidal mixture of claim 1 or 2, comprise other reactive compounds.
4. Fungicidal composition comprises the liquid or solid carrier and according to each mixture among the claim 1-3.
5. method of preventing and treating the plant-pathogenic harmful fungoid comprises and handles plant, soil or the seed that fungi, its habitat maybe will prevent fungal attack with the Synergistic effective dose according to the Compound I of claim 1 and Compound I I.
6. according to the method for claim 5, wherein simultaneously, i.e. associating or separately, or use Compound I and II successively according to claim 1.
7. according to the method for claim 5 or 6, wherein use according to the Compound I of claim 1 and II or according to each mixture among the claim 1-4 with the amount of 5-2000g/ha.
8. according to the method for claim 5 or 6, wherein use according to the Compound I of claim 1 and II or according to each mixture among the claim 1-3 with the amount of 1-1000g/100kg seed.
9. according to the method for claim 5 or 6, wherein prevent and treat Phakopsora (Phakopsara).
10. seed comprises according to each mixture among the claim 1-3 with the amount of 1-1000g/100kg.
11. Compound I and II according to claim 1 are preparing according to the purposes in the composition of claim 4.
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CN105724393A (en) * 2016-04-07 2016-07-06 陕西上格之路生物科学有限公司 Application of bactericidal compound containing metconazole to preventing wheat scab
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CN101959413A (en) * 2008-02-28 2011-01-26 先正达参股股份有限公司 Pesticidal combinations
CN102067859A (en) * 2011-02-19 2011-05-25 陕西美邦农药有限公司 Bactericidal composition containing ipconazole and thiocarbamate compound
CN105724393A (en) * 2016-04-07 2016-07-06 陕西上格之路生物科学有限公司 Application of bactericidal compound containing metconazole to preventing wheat scab
CN105724393B (en) * 2016-04-07 2018-06-05 陕西上格之路生物科学有限公司 Application of the bactericidal composition containing metconazole in prevention wheat scab
CN106719767A (en) * 2017-01-17 2017-05-31 上海悦联生物科技有限公司 A kind of composition pesticide containing metconazole and Prochloraz

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